Diphenylmethane azo dyestuffs and process of making same



Patented Oct. 30, 1928.

UNITED STATES PATE "OFFICE on" AsnL, SWITZERLAND.

nIriIENYLMn'rnANE AZO nynsmnrrs AND rnoc-Ess or MAKING'SAME.

in Drawing. a pncauon fled January'14,'1927, Serial No. 161,240,,and in Germany January as, im.

' not to be expected.-

When aniline reacts with chloro nethylortho-cresotinic acid, there. is obtamed In good yield anilinta-methylenebrtho-creso- GOOH Like derivatives of diphenylmethane are Obtained whenthere is used instead of aniline another amine of the benzene or naphthalene series, and instead of chloromethyl-ortho- 'cresotinic acid another chloromethyld eriva-I, tive of an ortho-hydroxy--carbo2iylic 301d.

Hitherto these compounds have not found application in the manufacture of dyestufisl By the present invention a new series of mordant dyeing azo-dyestuffs is obtained by diazotizing a derivative of a diphenylme- The dyestuffs thus made are valuable because when achromium salt'is' added they yield in cotton printing red and violet tints which are as vivid as those which'hitherto have been produced by the dyestuffs of the triphenylmethane series; at the-same time the tints have very good fastness to washing, :chlorine and light. on the other hand, wool dyestufi's can be made which yield d eings that when afterchromed are fast to ulling ,and potting. Finally, these dyestuffs are suitable for'making lakes.

That the diphenylmethanes in question could be used for a smooth production of a20- d'y'estufi's was not to be expected; for nitrous acid frequently acts to decompose such diphenylmethanes having two auxochrome groups in paraor ortho-position to the methane residue, or to oxidize them at the meth-' ane group '(see German patent specification No. 245,769). The production of such pure tints with these mordant dyestufis was The following example illustrates the invention 20 kilos of chloromethyl-ortho-cresotinic acid (see German patent specification No. 236,046) are boiledvwith 200 litres of water and 18.6 kilos of anilinefor 16 hours in a renci on equation coon flux apparatus. When the mass has cooled it cam. METTLER, or BASEL, SWITZERLAND, assrclyon 'ro transmit .1. '3. claim: A. 6.1

is made alkaline with sodium carbonate and the unaltered aniline'is' distilled in steam."

By addition ofhydrochloric acid the anilinemethylene-ortho-cresotinic acid isf precip'itated, -When dryit is'a colorlessYpowder,

which is insoluble in water but passes into so lution on addition of sodium. carbonate or of an excess ofhydrochloric acid, I

A quantity ofthe aniline-methyleneorthocresotinic acid corresponding with 6.9 kilos of sodium nitrite isdiazotized in cold hydrochloric acid and coupled in solution alkaline with sodium carbonate with the sodium salt of 28.8 kilos of 1(2 chloro-5-sulphophenyl)5 3-methyl-5-pyrazoldne. After stirring. during 24'hours, the:wh-ole is warmed up and the dyestufi is precipitated by means of common salt as a yellow precipitate. When dried, the dyestuif constitutes a yellow powder, which is difiicultly soluble in cold. water, easily-soluble' in hot water with a greenish-yellow coloration and'also soluble inconcentrated sulphuric acid with a yellow coloration; It dyes wool from an acetic acid bath of greenish-yellow tints which are fast to acid;

By subsequent chromati'oh, the coloration.

changes more to yellow.

The product obtained ample may have the following formula:

OHa I 5 I HO CHO FiH i according to this ex- BOz any other amind-diphenylmethanederivative ,may beused, which canbe obtained by reaction of an amine of the benzene or naphthalene series with a chloromethyl-deriyatiye' of 'i an aromatic ortho-hydro -carbo such as salicylic acid, 31 ha ogensu product of such an acid, an ortho-,hydroxy-' he acid, itution carbox'ylic acid of the naphthalene series etc. In eneral,"any diphenylmethane derivative of t e kind described may be used.

firrnents named. any other components of this (1 may be used whereby dyestufis of V6? difl'erent tints and fa'stness are obtaine When 1-naphto1-3: 6-disulphonic acid is used a brown red dyestufi' can be obtained which is easily soluble in water t: a yellow-red solution and in concentrated sulphuric acid to a; ich,whenprint- .ed on cotton 'with a chromium salt, gives a yellowish-red solution, and w azotizing a diphenyl-methane derivative whichcontains in one nucleus an amino-group I and in the other an 'ortho-hydroxy-carboxylic also instead of the azo-dyestufi' coniacid group, and coupling with ana'zo-jdyestufl component.

2. Aprocess forthe manufacture of m0rdent dyeing azo-dyestufi's, consisting indiazotizin aniline-methylene-ortho-cresotinic acid-an coupling with anvazo-dyestufi component. v 3. A process for the manufacture of mordant dyeing azo-dyestufi's, consisting in diazotizin acid an coupling with 1(2-chloro-5-sulphoaniline-methyleneortho cresotinic pheny'l)-3 methy1-5-pyrazolonein alkaline so ution.

4. As a new hereinbefore described mordant dyeing dyestuffs obtained by diazotizing aniline-methylene-ortho-cresotinic acid and couplin wlth 1(2-ch1oro-5-sulphophen l) -3'-methy -5-pyrazolone, constituting in cm of its sodium salt a yellow powder diflicultly soluble in cold" article of manufacture, the-- water, easily soluble in hot water with a greenish-yellow color, in concentrated sulphuric acid with a yellow color, dyeing wool from an acetic acid bath greenish-yellow tints,

which after chromation change more to yellow.

In w tness whereof I have hereunto signed my name this 30th day of December, 1926.

CARL METTLER. 

